CN108159477B - Preparation method and application of anticoagulant and anti-adhesion poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane - Google Patents
Preparation method and application of anticoagulant and anti-adhesion poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane Download PDFInfo
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- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention belongs to the field of biological materials, and particularly relates to a preparation method and application of an anticoagulant anti-adhesion agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane, wherein the method comprises the following steps: the preparation method is simple and easy to implement, the prepared nanofiber membrane has good blood compatibility and good anticoagulation and anti-adhesion effects, and the nanofiber membrane has a huge application prospect in preparation of medical dressings or stents suitable for contacting blood.
Description
Technical Field
The invention belongs to the field of biological materials, and particularly relates to a preparation method and application of an anticoagulant anti-adhesion agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane.
Background
Thromboembolic diseases have become the most dangerous and fatal diseases in humans. Blocking blood flow by forming clots in the blood vessels, platelet adhesion and aggregation are the "culprit" for thrombosis. The contact with blood after the implantation of any foreign material such as blood vessel, stent or organ will trigger a complex series of interactions (e.g. protein adsorption, platelet adhesion, activation and aggregation, activation of blood coagulation system and complement system, etc.) to form thrombus. Short-and long-term anticoagulants, such as heparin and argatroban, are often used to prevent thrombosis. The use of anticoagulant drugs can be reduced by combining the biological material with the anticoagulant, for example, the anticoagulant activity can be increased by using a blood vessel stent of polytetrafluoroethylene silk and polylactic acid membrane coated with heparin, and the dosage of the anticoagulant can be reduced; after the argatroban and the polyurethane-organic silicon polymer are connected, the anti-coagulation activity is increased by about 3.6 times as a cross-linked polymer coating; meanwhile, a polyvinylidene fluoride membrane can be grafted, so that the hemolysis rate is reduced, the plasma recalcification time is prolonged, and the partial thromboplastin activation time and the thrombin time are activated. However, long-term or large-scale use of anticoagulant drugs can cause blood coagulation dysfunction and even bleeding of the body. Therefore, the development of antithrombotic biomaterials without the use of anticoagulants is of great importance.
Most anticoagulant biomaterials without anticoagulants are prepared by surface chemical modification or modification of materials, but the process is complex and the manufacturing cost is high; meanwhile, the surface modification or modification of the biomaterial is to treat the solid surface, which usually results in uneven distribution of modified or modified groups, further affecting the anticoagulation effect and biocompatibility of the biomaterial.
Disclosure of Invention
The invention provides a preparation method of an anticoagulant and antiadhesion poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane for solving the problems, the method is simple and easy to implement, and the prepared membrane has uniform surface performance, good blood compatibility and good anticoagulant and antiadhesion effects.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the preparation method of the anticoagulant and anti-adhesion poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane comprises the following steps: the preparation method comprises the steps of adopting a 2,2,3,3,4,4, 4-heptafluoro butyl acrylate monomer to insert a fluorine-containing polymer chain segment at the end of a polycaprolactone macromolecular chain by a reversible addition fragmentation chain transfer method to form a poly-heptafluoro butyl acrylate-polycaprolactone segmented polymer, and carrying out electrostatic spinning on the poly-heptafluoro butyl acrylate-polycaprolactone segmented polymer to obtain the poly-heptafluoro butyl acrylate-polycaprolactone segmented polymer nanofiber membrane.
Preferably, the reversible addition fragmentation chain transfer method comprises the following two steps:
step 1, synthesizing trithiocarbonate terminated polycaprolactone (PCL-RAFT): in the presence of 4-Dimethylaminopyridine (DMF) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), taking Dichloromethane (DMF) as a solvent, and carrying out a chain transfer reaction on Polycaprolactone (PCL) with the molecular weight of 3-10 ten thousand and S-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate (RAFT reagent) to obtain trithiocarbonate terminated polycaprolactone;
step 2, synthesizing a hydrophobic poly (heptafluoro butyl acrylate) -polycaprolactone block polymer: in the presence of azodiisobutyronitrile, tetrahydrofuran is used as a solvent, and the trithiocarbonate terminated polycaprolactone obtained in the step 1 and 2,2,3,3,4,4, 4-heptafluorobutyl acrylate undergo a reversible addition-fragmentation reaction to obtain the poly-heptafluorobutyl acrylate-polycaprolactone block polymer (PCL-PHFBA).
Preferably, the step 1 is: heating polycaprolactone and S-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate at 60-80 ℃ for dehydration for 2-6h under vacuum, adding dimethylaminopyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, bubbling in nitrogen for 10-30min for degassing, adding anhydrous dichloromethane under nitrogen atmosphere to form a reaction system, after the polycaprolactone is dissolved, placing the reaction system at 20-40 ℃ for stirring for 2d, completing the reaction, adding a precipitation solvent into the reaction system, separating out a product, performing suction filtration, and performing vacuum drying to obtain trithiocarbonate-terminated polycaprolactone;
preferably, the precipitation solvent in step 1 is one or more of methanol, ethanol, isopropanol and hexane.
Preferably, in the step 2, the molecular weight of polycaprolactone is 8 ten thousand, the dehydration time is 4 hours, the degassing time is 20min, and the stirring time is 2 d.
Preferably, the step 2 is: dissolving trithiocarbonate-terminated polycaprolactone, heptafluorobutyl acrylate and azobisisobutyronitrile into a reaction system of tetrahydrofuran, bubbling and degassing the reaction system for 10-30min by using nitrogen, heating the reaction system to 50-70 ℃, reacting for 10-48h, cooling the reaction system to room temperature, adding isopropanol into the reaction system, separating out a product, filtering, purifying by using dimethylformamide, and drying in vacuum to obtain the heptafluorobutyl acrylate-polycaprolactone block polymer.
Preferably, in the reaction system in the step 2, the concentration of the trithiocarbonate-terminated polycaprolactone is 0.1g/mL, the concentration of the heptafluorobutyl acrylate is 0.01g/mL, the degassing time is 20min, the reaction temperature is 65 ℃, and the reaction time is 20 h.
Preferably, the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer is electrospun: dissolving the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer in a mixed solution of dichloromethane and dimethylformamide to obtain a spinning solution with the mass concentration of 5-10%, and performing electrostatic spinning on a metal collector at an injection rate of 0.5-2mL/h to obtain the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane, wherein the distance between the metal collector and an injector is 10-20 cm.
Preferably, in the electrostatic spinning, the volume ratio of dichloromethane to dimethylformamide is 4:1, the mass concentration of the spinning solution is 8%, the injection rate is 1mL/h, and the voltage is 20 kv.
Preferably, after the electrostatic spinning, the method further comprises the step of drying the poly-heptafluoro-butyl acrylate-polycaprolactone segmented polymer nanofiber membrane obtained by the electrostatic spinning in vacuum at the drying temperature of 20-50 ℃ for 12-24 h.
The application of the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane prepared by the invention in preparing medical dressings or stents suitable for contacting blood also belongs to the protection scope of the invention.
Preferably, the medical dressing or stent contacting blood refers to a medical dressing or stent applied to a blood vessel or a bleeding wound of a human body.
The invention has the beneficial effects that:
1. the invention adopts a reversible addition-fragmentation chain transfer polymerization method to synthesize a poly-heptafluoro-butyl acrylate-polycaprolactone segmented polymer nanofiber membrane, azodiisobutyronitrile is used as an initiator in the reversible addition-fragmentation chain transfer polymerization, and free radicals are generated in the initiation stage of the polymerization reaction and are subjected to chain transfer and propagation. The polycaprolactone macromolecular chain segment is extended and connected with the poly-heptafluoro-butyl acrylate short polymer chain segment, after the obtained block polymer is subjected to electrostatic spinning, the poly-heptafluoro-butyl acrylate block is spontaneously distributed on the surface layer of the nanofiber membrane due to low surface energy, the distribution is uniform, and meanwhile, the surface chemical grafting modification treatment after the electrostatic spinning is also avoided.
2. The polycaprolactone is selected as the base material of the material, and is widely reported to be used for controlled release drug carriers and bioengineering stents, and has the characteristics of controllable degradability, good mechanical properties, thermoplasticity and the like. Therefore, improving the blood compatibility of polycaprolactone is an advantageous choice for blood contacting devices.
3. The preparation process of the invention has no waste gas and waste liquid, is environment-friendly, and has simple and easy operation and low cost.
4. The invention increases the hydrophobicity of polycaprolactone by introducing the fluorinated polymer, and finally improves the hydrophobicity of polycaprolactone by taking the 2,2,3,3,4,4, 4-heptafluorobutyl acrylate short fluorocarbon as the fluorinated polymer, thereby avoiding the environmental problem caused by using long fluorocarbon and having low cost.
5. The invention adopts electrostatic spinning to prepare the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane, the diameter of the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane is controllable, the specific surface area of the membrane can be increased, the biocompatibility is good, the blood compatibility is good, the anti-adhesion effect is good, and the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane can be used for stent materials or dressings which contact blood.
Drawings
FIG. 1 is a scanning electron microscope image of 1 ten thousand times of an anticoagulant antiadhesive agglomerated heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane prepared in accordance with the present invention; wherein, (a) is a surface structure topography map of the polycaprolactone film, and (b) is a surface structure topography map of the heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber film;
FIG. 2 is a contact angle diagram of an anticoagulant antiadhesive agglomerated heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane prepared in accordance with the present invention, wherein (a) is a contact angle diagram of polycaprolactone membrane; (b) is a contact angle diagram of a heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane; (c) a statistical analysis chart for the two;
FIG. 3 is a graph comparing the results of blood compatibility of prepared anticoagulant antiadhesive agglomerated heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membranes, wherein (a) is a comparison of the hemolysis rate statistical analysis of the two membranes; (b) comparing the two membranes with the whole blood agglutination time; (c) plasma recalcification time statistical analysis chart for two membranes; (d) a statistical analysis chart of the activated prothrombin time of two membranes; (e) statistical analysis of plasma prothrombin time for both membranes;
FIG. 4 is a comparison of platelet adhesion of the prepared anticoagulant antiadhesion agglomerated heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane; (a) a polycaprolactone membrane adhesion platelet graph, and (b) a polyheptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane adhesion platelet graph;
FIG. 5 is a comparison of the cell compatibility of the prepared anticoagulant antiadhesive agglomerated heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane;
FIG. 6 is a graph comparing the anti-adhesion ability of the prepared anticoagulant anti-adhesion agglomerated heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane; (a) adhering FITC marked bovine serum albumin fluorescence imaging images to the two films; (b) is a statistical analysis chart of the BCA kit protein after the bovine serum albumin is adhered to two membranes and the protein is quantified.
FIG. 7 is a reaction scheme of a reversible addition fragmentation chain transfer process.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The first embodiment is as follows: a preparation method of an anticoagulant antiadhesive agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane comprises the following steps:
(1) synthesis of Trithiocarbonate-terminated polycaprolactone: 5g of polycaprolactone and 0.182g S-dodecyl-S '- (alpha, alpha' -dimethyl-alpha "-acetic acid) trithiocarbonate were placed in a 100mL flask and heated at 80 ℃ for 2 hours under vacuum to remove water. Then adding 30mg of dimethylaminopyridine and 95mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) into nitrogen, bubbling for 20min, degassing, adding 60mL of anhydrous dichloromethane under the protection of nitrogen, stirring the solution at 40 ℃ for 2 days after the polycaprolactone is dissolved, precipitating the product by using 300mL of methanol, dissolving the product in dichloromethane again, precipitating again, repeating twice, and drying and collecting the final product in vacuum;
(2) synthesizing hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving 1g of trithiocarbonate terminated polycaprolactone, 0.1g of heptafluoro-butyl acrylate and 0.37mg of azobisisobutyronitrile in a single-neck round flask containing 10mL of tetrahydrofuran, degassing the solution by bubbling with nitrogen for 20min, placing the solution in an oil bath at 65 ℃ for 20h, cooling with cold water to terminate the reaction, precipitating the product with 100mL of isopropanol, dissolving the product with 20mL of dimethylformamide, centrifuging at 4000rpm, precipitating the clear solution in 100mL of isopropanol again, and finally vacuum-drying at room temperature;
(3) electrostatic spinning hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer in a mixed solution of dichloromethane and dimethylformamide, wherein the concentration is 8%, and performing electrostatic spinning on a metal collector (15cm to an injector) at an injection rate of 1mL/h under a voltage of 20 kv;
(4) and (3) drying: and (2) placing the spun poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane in the step 3) into a vacuum oven, and drying for 16 hours at the temperature of 40 ℃ to obtain the anticoagulant anti-adhesion agglomerated poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane, wherein the size of the nanofiber of the membrane is 0.15 mu m (see figure 1).
The bio-contact angles of the nanofiber membrane and the polycaprolactone membrane obtained in example 1 were measured (see fig. 2), the average contact angle of the polycaprolactone membrane was 115 °, and the average contact angle of the heptafluorobutylacrylate-polycaprolactone block polymer nanofiber membrane was 136 °.
Example two: a preparation method of an anticoagulant antiadhesive agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane comprises the following steps:
(1) synthesis of Trithiocarbonate-terminated polycaprolactone: 2g of polycaprolactone and 72.8mg of S-dodecyl-S '- (alpha, alpha' -dimethyl-alpha "-acetic acid) trithiocarbonate were placed in a 50mL flask and heated at 70 ℃ for 4 hours under vacuum to remove water. Then adding 12mg of dimethylaminopyridine and 32mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) into nitrogen, bubbling for 20min, degassing, adding 20mL of anhydrous dichloromethane under the protection of nitrogen, stirring the solution at room temperature for 2 days after the polycaprolactone is dissolved, precipitating the product by using 100mL of ethanol, dissolving the product in dichloromethane again, precipitating again, repeating twice, and collecting the final product under vacuum drying;
(2) synthesizing hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving 0.5g of trithiocarbonate terminated polycaprolactone, 0.05g of heptafluoro-butyl acrylate and 0.18mg of azobisisobutyronitrile in a single-neck round flask containing 5mL of tetrahydrofuran, bubbling the solution with nitrogen for 20min for degassing, then placing in an oil bath at 60 ℃ for 24 hours, cooling with cold water to terminate the reaction, precipitating the product with 50mL of isopropanol, and drying in vacuum at room temperature;
(3) electrostatic spinning hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer in a mixed solution of dichloromethane and dimethylformamide with the concentration of 5%, and performing electrostatic spinning on a metal collector (15cm to an injector) at the injection rate of 0.8mL/h under the voltage of 20 kv;
(4) and (3) drying: placing the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane spun in the step 3) in a vacuum oven, and drying for 12 hours at the temperature of 45 ℃ to obtain an anticoagulant anti-adhesion agglomerated poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane, wherein the size of the nanofiber of the membrane is 0.15 mu m;
example three: a preparation method of an anticoagulant antiadhesive agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane comprises the following steps:
(1) synthesis of Trithiocarbonate-terminated polycaprolactone: 5g of polycaprolactone and 0.182g S-dodecyl-S '- (alpha, alpha' -dimethyl-alpha "-acetic acid) trithiocarbonate were placed in a 100mL flask and heated at 60 ℃ under vacuum for 6 hours to remove water. Then adding dimethylaminopyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) into nitrogen, bubbling for 20min, degassing, adding 60mL of anhydrous dichloromethane under the protection of nitrogen, stirring the solution at 30 ℃ for 2 days after the polycaprolactone is dissolved, precipitating the product by using isopropanol, dissolving the product in dichloromethane again, precipitating again, repeating twice, and collecting the final product under vacuum drying;
(2) synthesizing hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving 2g of trithiocarbonate terminated polycaprolactone, 0.2g of heptafluoro-butyl acrylate and 0.74mg of azobisisobutyronitrile in a single-neck round flask containing 20mL of tetrahydrofuran, degassing the solution by bubbling with nitrogen for 20min, then placing the solution in an oil bath at 70 ℃ for 12 h, cooling with cold water to terminate the reaction, precipitating the product with isopropanol, dissolving the product with 30mL of dimethylformamide, centrifuging at 6000rpm, precipitating the clear solution in 150mL of isopropanol again, and finally drying in vacuum at room temperature;
(3) electrostatic spinning hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer in a mixed solution of dichloromethane and dimethylformamide with the concentration of 10%, and performing electrostatic spinning on a metal collector (15cm to an injector) at the injection rate of 0.5mL/h under the voltage of 20 kv;
(4) and (3) drying: placing the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane spun in the step 3) in a vacuum oven, and drying for 24 hours at the temperature of 65 ℃ to obtain an anticoagulant anti-adhesion agglomerated poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane, wherein the size of the nanofiber of the membrane is 0.15 mu m;
example four: a preparation method of an anticoagulant antiadhesive agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane comprises the following steps:
(1) synthesis of Trithiocarbonate-terminated polycaprolactone: 1g of polycaprolactone and 36.4mg of S-dodecyl-S '- (alpha, alpha' -dimethyl-alpha "-acetic acid) trithiocarbonate were placed in a 50mL flask and heated at 80 ℃ for 2 hours under vacuum to remove water. Then 6mg dimethylaminopyridine and 16mg 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) are added and degassed by bubbling in nitrogen for 30min, 10mL of anhydrous dichloromethane are added under nitrogen protection, after the polycaprolactone is dissolved, the solution is stirred at 35 ℃ for 2 days, the product is precipitated with 50mL of hexane, the product is redissolved in dichloromethane and precipitated again, the process is repeated twice, and the final product is collected under vacuum drying;
(2) synthesizing hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving 0.5g of trithiocarbonate terminated polycaprolactone, 0.05g of heptafluoro-butyl acrylate and 0.18mg of azobisisobutyronitrile in a single-neck round flask containing 5mL of tetrahydrofuran, bubbling the solution with nitrogen for 30min for degassing, then placing the solution in an oil bath at 55 ℃ for 36 hours, cooling with cold water to terminate the reaction, precipitating the product with 50mL of isopropanol, and drying in vacuum at room temperature;
(3) electrostatic spinning hydrophobic poly-heptafluoro-butyl acrylate-polycaprolactone block polymer, dissolving the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer in a mixed solution of dichloromethane and dimethylformamide with the concentration of 6%, and performing electrostatic spinning on a metal collector (15cm to an injector) at the injection rate of 1.5mL/h under the voltage of 20 kv;
(4) and (3) drying: placing the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane spun in the step 3) in a vacuum oven, and drying for 16 hours at the temperature of 50 ℃ to obtain an anticoagulant anti-adhesion agglomerated poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane, wherein the size of the nanofiber of the membrane is 0.15 mu m;
example five: to examine the blood compatibility of the prepared anticoagulation anti-adhesion agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane, the following experiment was performed.
(1) Hemolysis assay
Experimental grouping: control group: a polycaprolactone film; experimental groups: a poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane;
cutting the polycaprolactone film and the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber film into a film with the size of 1 x 2.5 cm;
③ washing with deionized water for 5 times, and washing with physiological saline for 3 times;
fourthly, putting the membrane into 10mL of physiological saline, carrying out water bath at 37 ℃ for 30min, respectively adding 200 mu L of diluted whole blood, incubating for 1 hour at 37 ℃, taking the physiological saline as a negative control, and taking the distilled water as a positive control;
centrifuging at 1500 rpm for 10min, and reading OD value of the supernatant at 545nm with an enzyme-labeling instrument: the hemolysis rate was calculated according to this equation: hemolysis rate [% OD experimental group-OD negative group ]/[ OD positive group-OD negative group ] × 100;
(2) coagulation time of whole blood
Experimental grouping: control group: a polycaprolactone film; experimental groups: a poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane;
cutting the polycaprolactone film and the poly heptafluoro butyl acrylate-polycaprolactone block polymer nanofiber film into 2 x 2 cm-sized films;
③ washing 5 times with deionized water, washing 3 times with normal saline, and then putting into a culture dish;
0.5mL of each group of fresh rabbit blood (without anticoagulant) was dropped onto the membrane, and the membrane was tilted 30 degrees every 30 seconds until the blood no longer flowed, and the time was recorded.
(3) In vitro coagulation test
Experimental grouping: control group: a polycaprolactone film; experimental groups: a poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane;
cutting the polycaprolactone film and the poly heptafluoro butyl acrylate-polycaprolactone block polymer nanofiber film into a film with the size of 1 x 1 cm;
thirdly, incubating the membrane and normal saline for 30min in water bath at 37 ℃;
fourthly, incubating the culture medium with the platelet-poor plasma in water bath at 37 ℃ for 60 min;
collecting supernatant, and detecting the activated thrombin time and the plasma prothrombin time by an automatic coagulation analyzer.
(4) Plasma recalcification time
Experimental grouping: control group: a polycaprolactone film; experimental groups: a poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane;
cutting the polycaprolactone film and the poly heptafluoro butyl acrylate-polycaprolactone block polymer nanofiber film into a film with the size of 1 x 1 cm;
thirdly, incubating the membrane and normal saline for 30min in water bath at 37 ℃;
fourthly, incubating the culture medium with the platelet-poor plasma in water bath at 37 ℃ for 60 min;
adding 300 μ L of 0.025mol/L calcium chloride solution, gently mixing, inclining for 30 degrees every 10s until the blood does not flow, and recording the time.
The experimental results of example 5 are shown in FIG. 3, in which (a) is a comparison graph of the blood hemolysis rates of both membranes, which are less than 5% and are considered to have good blood compatibility, and the average value of the blood hemolysis rate of the PBA-polycaprolactone block polymer nanofiber membrane is 1 and is significantly lower than that of the polycaprolactone membrane, (b) is a comparison graph of the whole blood coagulation time of both membranes, which is 225 seconds, and the average whole blood coagulation time of PBA-polycaprolactone block polymer nanofiber membrane is 302 seconds, which are significantly longer than that of the conventional control group 194 seconds, and (c) is a comparison graph of the plasma recalcification time of both membranes, which are 295 seconds, respectively, 303 seconds and 311 seconds, after statistical analysis, the plasma recalcification time of the poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane is significantly different from that of the control group, which shows that: the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane has good anticoagulation performance, (d) is a statistical analysis graph of activated prothrombin time of two membranes, the activated prothrombin time of the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane is obviously longer than that of a control group and a polycaprolactone membrane, and the result shows that the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane has good anticoagulation performance, and (e) is a statistical analysis graph of plasma prothrombin time of the two membranes, and the result shows that the anticoagulation activity of the poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane is obviously better than that of the polycaprolactone membrane.
Example six: to examine the platelet adhesion of the prepared anticoagulation antiadhesion agglomerated heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane, the following experiment was performed.
1) Grouping experiments: control group: a polycaprolactone film; experimental groups: a poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane;
2) preparing a polycaprolactone film and a poly (heptafluoro butyl acrylate) -polycaprolactone segmented polymer nanofiber film into a film with the diameter of 0.6 cm;
3) incubating the membrane with normal saline in a water bath at 37 ℃ for 30 min;
4) then incubating with platelet rich plasma in water bath at 37 ℃ for 2 hours;
5) washing the membrane for 3 times by phosphate buffer, and fixing by glutaraldehyde for 24 hours;
6) and (5) observing by a scanning electron microscope after gradient dehydration and gold spraying.
The scanning electron microscope is shown in figure 4, wherein (a) is a polycaprolactone membrane-adhered platelet map, and (b) is a polyheptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane-adhered platelet map, the platelet adhesion number of the both is small, and the adhesion resistance of the polyheptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane is higher than that of polycaprolactone.
Example seven: to examine the cell compatibility of the prepared anticoagulation anti-adhesion agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane, the following experiment was performed.
1) Grouping experiments: common control group: a polycaprolactone film; experimental groups: a poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane; positive control group: cell climbing sheet
2) Preparing a polycaprolactone film and a poly (heptafluoro butyl acrylate) -polycaprolactone segmented polymer nanofiber film into a film with the diameter of 0.6 cm; sterilizing with 75% ethanol for 30min, and washing with phosphate buffer solution for 3 times;
2) placing the treated membrane in a 96-well plate, adding vascular endothelial cells (the density is 3000 per hole) in a logarithmic growth phase, and removing the original culture medium after the cells grow in an adherent manner for 24 hours;
3) culturing for 24 hours and 72 hours respectively to perform cell proliferation detection experiments, taking out the membrane, placing the membrane in a new 96-well plate, adding 100 mu L of new culture medium and 10 mu L of LCCK8 reagent into each well, and incubating for 2 hours at 37 ℃;
4) and (5) detecting the absorbance of each hole at the wavelength of 450nm by using a microplate reader, and performing statistical analysis.
Example 7 results referring to fig. 5, it can be seen that the number of cells in the pbac-polycaprolactone segmented polymer nanofiber membrane was smaller than that in the polycaprolactone membrane after 24 hours of co-culture of the membrane and the cells, but the number of cells in the 2 groups was not different after 72 hours. This is probably due to the fact that the number of cells adhering to the polyheptafluorobutylacrylate-polycaprolactone block polymer nanofiber membrane at 24 hours is less than that of polycaprolactone membrane.
Example eight: to examine the anti-protein adhesion of the prepared anticoagulation anti-adhesion agglomeration heptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane, the following experiment was performed.
1) Grouping experiments: control group: a polycaprolactone film; experimental groups: a poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane;
2) preparing a polycaprolactone film and a poly (heptafluoro butyl acrylate) -polycaprolactone segmented polymer nanofiber film into a film with the diameter of 0.6 cm;
3) washing with deionized water for 3 times;
4) the membrane was incubated with bovine serum albumin (1mg/mL) and FITC-labeled bovine serum albumin (1mg/mL) at 37 ℃ for 2 hours, respectively;
5) washing the membrane with deionized water for 3 times;
6) and (3) quantifying the protein of the membrane incubated with the bovine serum albumin by using a BCA kit, detecting an OD value by using an enzyme-labeling instrument, and observing the membrane incubated with the FITC-labeled bovine serum albumin by using laser confocal technology.
The experimental results of example 8 are shown in fig. 6, wherein (a) is a fluorescence imaging graph of two kinds of membranes adhered with FITC labeled bovine serum albumin, the amount of the fluorescent labeled protein adhered to the polyheptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane is significantly less than that of the polycaprolactone membrane, and (b) is a statistical analysis graph of the quantified BCA kit protein after two kinds of membranes are adhered with bovine serum albumin, and the results show that the amount of the protein adhered to the polyheptafluorobutyl acrylate-polycaprolactone block polymer nanofiber membrane is significantly less than that of the polycaprolactone membrane.
The foregoing lists merely illustrate specific embodiments of the invention. It is obvious that the invention is not limited to the above-described embodiments, but that many combinations of operations are possible. All matters hithertofore set forth or suggested by those skilled in the art, including the description herein, are to be understood as being within the scope of the invention.
Claims (12)
1. The preparation method of the anticoagulant and anti-adhesion poly-heptafluoro-butyl acrylate-polycaprolactone block polymer nanofiber membrane is characterized by comprising the following steps of: the preparation method comprises the steps of adopting a 2,2,3,3,4,4, 4-heptafluoro butyl acrylate monomer to insert a fluorine-containing polymer chain segment at the end of a polycaprolactone macromolecular chain by a reversible addition fragmentation chain transfer method to form a poly-heptafluoro butyl acrylate-polycaprolactone segmented polymer, and carrying out electrostatic spinning on the poly-heptafluoro butyl acrylate-polycaprolactone segmented polymer to obtain the poly-heptafluoro butyl acrylate-polycaprolactone segmented polymer nanofiber membrane.
2. The method of claim 1, wherein the reversible addition fragmentation chain transfer method comprises the two steps of:
step 1: synthesis of Trithiocarbonate-terminated polycaprolactone: in the presence of 4-dimethylaminopyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, taking methylene dichloride as a solvent, and carrying out a chain transfer reaction on polycaprolactone with the molecular weight of 3-10 ten thousand and S-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate to obtain trithiocarbonate terminated polycaprolactone;
step 2: synthesizing hydrophobic poly (heptafluoro butyl acrylate) -polycaprolactone block polymer: in the presence of azodiisobutyronitrile, tetrahydrofuran is used as a solvent, and the trithiocarbonate terminated polycaprolactone obtained in the step 1 and 2,2,3,3,4,4, 4-heptafluorobutyl acrylate undergo a reversible addition-fragmentation reaction to obtain the polyheptafluorobutyl acrylate-polycaprolactone block polymer.
3. The method of claim 2, wherein step 1 is: heating and dehydrating polycaprolactone and S-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate at 60-80 ℃ for 2-6h under vacuum, adding 4-dimethylaminopyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, bubbling in nitrogen for 10-30min for degassing, adding anhydrous dichloromethane to form a reaction system under the nitrogen atmosphere, after the polycaprolactone is dissolved, placing the reaction system at 20-40 ℃ for stirring for 2d, completing the reaction, adding a precipitation solvent into the reaction system, separating out a product, performing suction filtration, and performing vacuum drying to obtain the trithiocarbonate-terminated polycaprolactone.
4. The method according to claim 3, wherein the precipitation solvent in step 1 is one or more selected from the group consisting of methanol, ethanol, isopropanol, and hexane.
5. The preparation method according to claim 3, wherein in the step 1, the molecular weight of polycaprolactone is 8 ten thousand, the dehydration time is 4h, and the degassing time is 20 min.
6. The method according to any one of claims 2 to 4, wherein the step 2 is: dissolving trithiocarbonate-terminated polycaprolactone, 2,3,3,4,4, 4-heptafluorobutyl acrylate and azobisisobutyronitrile into a reaction system of tetrahydrofuran, bubbling and degassing the reaction system for 10-30min by using nitrogen, heating the reaction system to 50-70 ℃, reacting for 10-48h, cooling the reaction system to room temperature, adding isopropanol into the reaction system, separating out a product, filtering, purifying by using dimethylformamide, and drying in vacuum to obtain the heptafluorobutyl acrylate-polycaprolactone block polymer.
7. The method according to claim 6, wherein the reaction system in the step 2 has a trithiocarbonate-terminated polycaprolactone concentration of 0.1g/mL, a 2,2,3,3,4,4, 4-heptafluorobutylacrylate concentration of 0.01g/mL, a degassing time of 20min, a reaction temperature of 65 ℃ and a reaction time of 20 hours.
8. The method according to any one of claims 2 to 5, wherein the poly (heptafluorobutyl acrylate) -polycaprolactone block polymer is electrospun: dissolving the poly (heptafluoro-butyl acrylate) -polycaprolactone block polymer in a mixed solution of dichloromethane and dimethylformamide to obtain a spinning solution with the mass concentration of 5-10%, and performing electrostatic spinning on a metal collector at an injection rate of 0.5-2mL/h to obtain the poly (heptafluoro-butyl acrylate) -polycaprolactone block polymer nanofiber membrane, wherein the distance between the metal collector and an injector is 10-20 cm.
9. The production method according to claim 8, wherein in the electrospinning, the volume ratio of dichloromethane to dimethylformamide is 4:1, the mass concentration of the spinning dope is 8%, the injection rate is 1mL/h, and the voltage of the electrospinning is 20 kv.
10. The preparation method according to any one of claims 2 to 5, wherein after the electrospinning, the method further comprises vacuum drying the poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane obtained by the electrospinning at the drying temperature of 20-50 ℃ for 12-24 h.
11. Use of a poly (heptafluorobutyl acrylate) -polycaprolactone segmented polymer nanofiber membrane prepared by the preparation method of any one of claims 1-10 in the preparation of a medical dressing or stent suitable for contacting blood.
12. The use of claim 11, wherein said blood-contacting medical dressing or stent is a medical dressing or stent applied to a blood vessel or bleeding wound of a human body.
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